全文获取类型
收费全文 | 34465篇 |
免费 | 5281篇 |
国内免费 | 3845篇 |
专业分类
化学 | 24513篇 |
晶体学 | 400篇 |
力学 | 2029篇 |
综合类 | 258篇 |
数学 | 4016篇 |
物理学 | 12375篇 |
出版年
2024年 | 109篇 |
2023年 | 617篇 |
2022年 | 1103篇 |
2021年 | 1227篇 |
2020年 | 1278篇 |
2019年 | 1214篇 |
2018年 | 1093篇 |
2017年 | 1002篇 |
2016年 | 1525篇 |
2015年 | 1554篇 |
2014年 | 1885篇 |
2013年 | 2507篇 |
2012年 | 2955篇 |
2011年 | 3122篇 |
2010年 | 2112篇 |
2009年 | 2082篇 |
2008年 | 2374篇 |
2007年 | 2165篇 |
2006年 | 1929篇 |
2005年 | 1589篇 |
2004年 | 1154篇 |
2003年 | 912篇 |
2002年 | 942篇 |
2001年 | 806篇 |
2000年 | 725篇 |
1999年 | 696篇 |
1998年 | 595篇 |
1997年 | 470篇 |
1996年 | 519篇 |
1995年 | 511篇 |
1994年 | 403篇 |
1993年 | 346篇 |
1992年 | 293篇 |
1991年 | 293篇 |
1990年 | 273篇 |
1989年 | 207篇 |
1988年 | 172篇 |
1987年 | 151篇 |
1986年 | 129篇 |
1985年 | 116篇 |
1984年 | 70篇 |
1983年 | 64篇 |
1982年 | 59篇 |
1981年 | 44篇 |
1980年 | 24篇 |
1979年 | 21篇 |
1978年 | 20篇 |
1977年 | 19篇 |
1976年 | 14篇 |
1974年 | 16篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
72.
醇体系中合成CuGaS2纳米晶及其形貌演变 总被引:1,自引:0,他引:1
以CuCl2·2H2O,自制的GaCl3和(NH2)2CS为原料,在乙二醇体系中合成了花状结构的CuGaS2纳米晶.产物分别用X射线粉末衍射仪、透射电子显微镜、场发射扫描电子显微镜、高分辩透射电子显微镜和X射线光电子能谱仪进行了表征.实验结果表明,220℃反应24 h得到均匀的花状纳米结构CuGaS2,它是由厚度80-100 nm的片晶组成.同时,通过反应时间的控制,可以清楚的看到由纳米颗粒到纳米球以及花状纳米结构的演变过程.另外,研究了反应温度、反应时间、溶剂等对产物和形貌的影响.此外,对花状结构纳米晶的生长机理进行了初步的探讨.室温荧光光谱表明,随粒径的降低,发光位发生了部分蓝移. 相似文献
73.
Li‐Ming Tang Yan‐Guo Li Wei‐Ping Ye Yue‐Sheng Li 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):5846-5854
Ethylene–propylene copolymerization, using [(Ph)NC(R2)CHC(R1)O]2TiCl2 (R1 = CF3, Ph, or t‐Bu; R2 = CH3 or CF3) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R1 and R2 influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R1 and R2, one complex (R1 = CF3; R2 = CH3) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with 13C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006 相似文献
74.
Chin‐Ping Yang Yu‐Yang Su Sheng‐Huei Hsiao 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):5909-5922
Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB ) were prepared from 2,6‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl‐substituted aromatic bis(ether amine)s by a standard two‐step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution‐cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass‐transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7‐substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6‐substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006 相似文献
75.
Huadong Tang Maciej Radosz Youqing Shen 《Journal of polymer science. Part A, Polymer chemistry》2006,44(22):6607-6615
Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006 相似文献
76.
Guey‐Sheng Liou Sheng‐Huei Hsiao Yi‐Kai Fang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(21):6466-6483
Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited Tg's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with Eonset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006 相似文献
77.
Der‐Jang Liaw Ching‐Cheng Huang En‐Tang Kang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2901-2911
Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl2(CHPh)[P(C6H11)3]2}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006 相似文献
78.
Cheng‐Ho Chen Chih‐Chun Teng Ming‐Shyong Tsai Fu‐Su Yen 《Journal of Polymer Science.Polymer Physics》2006,44(15):2145-2154
A Haake torque rheometer equipped with an internal mixer is used to study the influence of the amount of sodium montmorillonite (Na+‐MMT) and organically modified MMT (O‐MMT) on X‐ray diffraction (XRD), morphology, and mechanical characteristics of rigid poly (vinyl chloride) (PVC)/Na+‐MMT and PVC/O‐MMT nanocomposites, respectively. Results of XRD and transmission electron microscopy (TEM) indicate that MMT is partially encapsulated and intercalated in the rigid PVC/Na+‐MMT nanocomposites. However, results of XRD and TEM show MMT is partially intercalated and exfoliated in the rigid PVC/O‐MMT nanocomposites. Tensile strength, yield strength, and elongation at break of the rigid PVC/MMT nanocomposites were improved simultaneously with adding 1–3 wt % Na+‐MMT or O‐MMT with respect to that of pristine PVC. However, the addition of Na+‐MMT or O‐MMT should be kept as not more than 3 wt % to optimize the mechanical properties and the processing stability of the rigid PVC/MMT nanocomposites. SEM micrographs of the fractured surfaces of the rigid PVC/Na+‐MMT and PVC/O‐MMT nanocomposites both before and after tensile tests were also illustrated and compared. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2145–2154, 2006 相似文献
79.
A cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) film modified glassy carbon electrode (Co(II)TPP-GCE) was prepared by just coating Co(II)TPP solution on the surface of the electrode. It can be used for the simultaneous determination of ascorbic acid and uric acid. The anodic peaks of AA and UA can be separated well. Owing to the strongly hydrophobic property of porphyrin, the modified electrode has good stability and long life. The linear range for UA and AA were 2.0 x 10(-6)-1.0 x 10(-4) M and 9.0 x 10(-6)-2.0 x 10(-3) M with detection limits of 5.0 x 10(-7) and 5.0 x 10(-6) M, respectively. Furthermore, metalloporphyrins of other kinds were also used to construct modified electrodes. Their performances were inferior compared with that of the Co(II)TPP modified electrode. 相似文献
80.
In this paper we study the stability of transonic shocks in steady supersonic flow past a wedge. We take the potential flow equation as the mathematical model to describe the compressible flow. It is known that in generic case such a problem admits two possible location of shock, connecting the flow ahead it and behind it. They can be distinguished as supersonic-supersonic shock and supersonic-subsonic shock (or transonic shock). Both these possible shocks satisfy the Rankine-Hugoniot conditions and entropy condition. In this paper we prove that the transonic shock is also stable under perturbation of the coming flow provided the pressure at infinity is well controlled. 相似文献